Method for manufacturing solar cell and dopant layer thereof

ABSTRACT

A method for manufacturing a dopant layer of a solar cell according to an embodiment of the invention includes: ion-implanting a dopant to a substrate; and heat-treating for an activation of the dopant. In the heat-treating for the activation, the substrate is heat-treated at a first temperature after an anti-out-diffusion film is formed at a temperature lower than the first temperature under a first gas atmosphere.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to and the benefit of Korean PatentApplication No. 10-2012-0067537, filed on Jun. 22, 2012 in the KoreanIntellectual Property Office, the disclosure of which is incorporatedherein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the invention relate to a method for manufacturing asolar cell and a dopant layer thereof. More particularly, the inventionrelates to a method for manufacturing a dopant layer having enhancedproperties and to a method for manufacturing a solar cell including thesame.

2. Description of the Related Art

Recently, as existing energy resources such as oil or coal are expectedto be exhausted, an interest in alternative energy resources forreplacing oil or coal is increasing. In particular, a solar cell thatdirectly converts or transforms solar energy into electricity using asemiconductor element is gaining attention as a next-generation energydevice.

In a solar cell, a p-n junction is formed by forming a dopant layer ofan n-type or a p-type at a semiconductor substrate in order to inducephotoelectric conversion, and an electrode electrically connected to thedopant layer is formed. In order to form the dopant layer havingenhanced properties, dopants should be sufficiently doped to thesemiconductor substrate during a process for forming the dopant layer.However, since “out-diffusion” in which the dopants are diffused to anoutside of the semiconductor substrate is generated, a concentration ofthe dopant in the dopant layer may decrease and the dopant layer may nothave desired properties. If an additional treatment for preventing theout-diffusion is performed, a manufacturing cost may increase greatly.

SUMMARY OF THE INVENTION

The embodiments of the invention are directed to providing a method formanufacturing a dopant layer having enhanced properties with a highproductivity and to providing a method for manufacturing a solar cellincluding the same.

A method for manufacturing a dopant layer of a solar cell according toan embodiment of the invention includes steps of: ion-implanting adopant to a substrate; and heat-treating for an activation of thedopant. In the heat-treating for the activation, the substrate isheat-treated at a first temperature after an anti-out-diffusion film isformed at a temperature lower than the first temperature under a firstgas atmosphere.

A method for manufacturing a solar cell according to an embodiment ofthe invention includes: performing the above method to form the dopantlayer on the substrate; and forming an electrode electrically connectedto the dopant layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a solar cell according to anembodiment of the invention.

FIG. 2 is a block diagram for illustrating a method for manufacturing asolar cell according to an embodiment of the invention.

FIGS. 3 a to 3 h are cross-sectional views for illustrating the methodfor manufacturing the solar cell according to the embodiment of theinvention.

FIG. 4 is a graph illustrating a temperature with respect to time in astep for heat-treating for an activation of the method for manufacturingthe dopant layer according to the embodiment of the invention.

FIGS. 5 a to 5 e are cross-sectional views for illustrating a method formanufacturing a solar cell according to another embodiment of theinvention.

FIG. 6 is a cross-sectional view of a solar cell according to yetanother embodiment of the invention.

FIG. 7 is a graph of reflectance with respect to wavelength of solarcells manufactured by Experimental Embodiments 1 and 2, and ComparativeExample.

FIG. 8 is a graph of external quantum efficiency with respect towavelength of solar cells manufactured by Experimental Embodiments 1 and2, and Comparative Example.

FIG. 9 is a graph of internal quantum efficiency with respect towavelength of solar cells manufactured by Experimental Embodiments 1 and2, and Comparative Example.

FIG. 10 is an enlarged view of portion A of FIG. 9.

FIG. 11 is an enlarged view of portion B of FIG. 9.

FIG. 12 is a graph of sheet resistances of emitter of solar cellsaccording to Experimental Embodiments 1 and 2, and Comparative Example.

FIG. 13 is a graph of sheet resistances of back surface field layers ofsolar cells according to Experimental Embodiments 1 and 2, andComparative Example.

FIG. 14 is a graph of implied Voc of back surface field layers of solarcells according to Experimental Embodiments 1 and 2, and ComparativeExample.

FIG. 15 shows six solar cells manufactured according to ComparativeExample and twelve solar cells manufactured according to ExperimentalEmbodiment 1.

FIG. 16 is a graph of dopant concentration with respect to junctiondepths of emitter layers in solar cells manufactured according toExperimental Embodiment 3 and Comparative Example.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Hereinafter, embodiments of the invention will be described withreference to the accompanying drawings. However, the embodiments of theinvention are not limited to these embodiments, and variousmodifications of the embodiments are possible.

In order to clearly and concisely illustrate the embodiments of theinvention, elements not related to the embodiments of the invention areomitted in the figures. Also, elements similar to or the same as eachother have the same reference numerals in the figures whenever possibleor practical. In addition, dimensions of layers and regions areexaggerated or schematically illustrated, or some layers are omitted forclarity of illustration. In addition, the dimension of each part asdrawn may not reflect an actual size.

In the following description, when a layer or substrate “includes”another layer or portion, it can be understood that the layer orsubstrate can further include still another layer or portion. Also, whena layer or film is referred to as being “on” another layer or substrate,it can be understood that the layer of film is directly on the otherlayer or substrate, or intervening layers may also be present. Further,when a layer or film is referred to as being “directly on” another layeror substrate, it can be understood that the layer or film is directly onthe another layer or substrate, and thus, there is no intervening layer.

Hereinafter, a method manufacturing a dopant layer of a solar cell and amethod for manufacturing a solar cell according to embodiments of theinvention will be described with reference to the accompanying drawings.First, a solar cell manufactured by a method for manufacturing a solarcell according to embodiments of the invention will be described. Then,a method of manufacturing a dopant layer of a solar cell and a methodfor manufacturing a solar cell according to embodiments of the inventionwill be described.

FIG. 1 is a cross-sectional view of a solar cell according to anembodiment of the invention.

Referring to FIG. 1, a solar cell 100 according to an embodimentincludes a substrate 10 (for example, a semiconductor substrate 10),dopant layers 20 and 30 formed at the semiconductor substrate 10, andelectrodes 24 and 34 electrically connected to the semiconductorsubstrate 10 or the dopant layers 20 and 30. More specifically, thedopant layers 20 and 30 may include a first dopant layer (hereinafter,referred to as “an emitter layer”) 20 formed at or adjacent to a firstsurface (hereinafter, referred to as “a front surface”) of thesemiconductor substrate 10, and a second dopant layer (hereinafter,referred to as “a back surface field layer”) 30 formed at or adjacent toa second surface (hereinafter, referred to as “a back surface”) of thesemiconductor substrate 10. Also, the electrodes 24 and 34 may include afirst electrode (or a plurality of first electrodes) 24 electricallyconnected to the emitter layer 20, and a second electrode (or aplurality of second electrodes) 34 electrically connected to thesemiconductor substrate 10 or the back surface field layer 30. Inaddition, the solar cell 100 may further include an anti-reflectionlayer 22 and a passivation layer 32. This will be described in moredetail.

The semiconductor substrate 10 may include one or more of varioussemiconductor materials. For example, the semiconductor substrate 10 mayinclude silicon having a dopant of a second conductivity type. Singlecrystal silicon or polycrystalline silicon may be used for the silicon,and the second conductivity type may be an n-type. That is, thesemiconductor substrate 10 may include single crystal silicon orpolycrystalline silicon having a group V element, such as phosphorus(P), arsenic (As), bismuth (Bi), antimony (Sb), or the like.

When the semiconductor substrate 10 has the n-type dopant as in theabove, the emitter layer 20 of a p-type is formed at the front surfaceof the semiconductor substrate 10, thereby forming a p-n junctiontherebetween. When light, such as sun light, is incident to the p-njunction, electron-hole pairs are generated, and the electrons generatedby the photoelectric effect moves to the back surface of thesemiconductor substrate 10 and are collected by the second electrode 34,and the holes generated by the photoelectric effect moves to the frontsurface of the semiconductor substrate 10 and are collected by the firstelectrode 24. Then, electric energy is generated thereby.

In this instance, the holes having mobility lower than that of theelectrodes move to the front surface of the semiconductor substrate 10,not the back surface of the semiconductor substrate 10. Therefore, theconversion efficiency of the solar cell 100 can be enhanced.

The front and/or back surface of the semiconductor substrate 10 may be atextured surface to have protruded and/or depressed portions of variousshapes (such as a pyramid shape) or be an uneven surface. Thus, surfaceroughness is increased by the protruded and/or depressed portions, andreflectance of the incident sun light at the front surface of thesemiconductor substrate 10 can be reduced by the texturing. Then, anamount of the light reaching the p-n junction between the semiconductorsubstrate 10 and the emitter layer 20 can increase, thereby reducing anoptical loss of the solar cell 100. However, the embodiments of theinvention are not limited thereto, and thus, the protruded and/ordepressed portions may be formed at only one surface (especially, thefront surface), or there may be no protruded and/or depressed portionsat the front and back surfaces.

The emitter layer 20 including a first conductive type dopant may beformed at the front surface of the semiconductor substrate 10. A p-typedopant such as a group III element (for example, boron (B), aluminum(Al), gallium (Ga), indium (In) or the like) may be used for the firstconductive type dopant.

The anti-reflection layer 22 and the first electrode 24 may be formed onthe emitter 20 at the front surface of the semiconductor substrate 10.

The anti-reflection layer 22 may be formed substantially at the entirefront surface of the semiconductor substrate 10, except for the portionwhere the first electrode 24 is formed. The anti-reflection layer 22reduces reflectance (or reflectivity) of sun light incident to the frontsurface of the semiconductor substrate 10. Also, the anti-reflectionlayer 22 passivates defects at a surface or a bulk of the emitter layer20.

By reducing the reflectance of sun light incident to the front surfaceof the semiconductor substrate 10, an amount of the sun light reachingthe p-n junction formed between the semiconductor substrate 10 and theemitter layer 20 can be increased, thereby increasing a short circuitcurrent (Isc) of the solar cell 100. By passivating the defects at theemitter layer 20, recombination sites of minority carrier are reduced oreliminated, thereby increasing an open-circuit voltage (Voc) of thesolar cell 100. Accordingly, the open-circuit voltage and theshort-circuit current of the solar cell 100 can be increased by theanti-reflection layer 22, and thus, the efficiency of the solar cell 100can be enhanced.

The anti-reflection layer 22 may include one or more of variousmaterials. For example, the anti-reflection layer 22 may have a singlefilm structure or a multi-layer film structure including, for example,at least one material selected from a group consisting of siliconnitride, silicon nitride including hydrogen, silicon oxide, silicon oxynitride, aluminum oxide, MgF₂, ZnS, TiO₂ and CeO₂. However, theembodiments of the invention are not limited thereto, and thus, theanti-reflection layer 22 may include one or more of various materials.

The first electrode 24 is electrically connected to the emitter layer 20by penetrating the anti-reflection layer 22 at the front surface of thesemiconductor substrate 10. The first electrode 24 may include one ormore of various metals having high electrical conductivity. For example,the first electrode 24 may include silver (Ag) having high electricalconductivity. However, the embodiments of the invention are not limitedthereto.

Also, the back surface field layer 30 including the second conductivetype dopant with a concentration higher than that of the semiconductorsubstrate 10 is formed at the back surface of the semiconductorsubstrate 10. The back surface field layer 30 prevents or reduces therecombination of the electrons and holes at the back surface, and thus,enhances the efficiency of the solar cell 100. An n-type dopant such asa group V element (such as phosphorus (P), arsenic (As), bismuth (Bi),antimony (Sb), or the like) may be used as the second conductive typedopant.

The passivation layer 32 and the second electrode 34 may be formed atthe back surface of the semiconductor substrate 10.

The passivation layer 32 may be formed substantially at the entire backsurface of the semiconductor substrate 10, except for the portions wherethe second electrode 34 is formed. The passivation layer 32 passivatesdefects at the back surface of the semiconductor substrate 10, andeliminates the recombination sites of minority carrier. Thus, an opencircuit voltage of the solar cell 100 can be increased.

The passivation layer 32 may include a transparent insulating materialfor passing the light. Thus, the light can be incident to the backsurface of the semiconductor substrate 10 through the passivation layer32, thereby enhancing the efficiency of the solar cell 100. Thepassivation layer 32 may have a single film structure or a multi-layerfilm structure including, for example, at least one material selectedfrom a group consisting of silicon nitride, silicon nitride includinghydrogen, silicon oxide, silicon oxy nitride, aluminum oxide, MgF₂, ZnS,TiO₂ and CeO₂. However, the embodiments of the invention are not limitedthereto, and thus, the passivation film 32 may include one or more ofvarious materials.

The second electrode 34 may include a metal having a high electricconductivity. For example, the second electrode 34 may include silver(Ag) having high electrical conductivity and high reflectance. When thesilver having high reflectance is used, the light reaching the backsurface of the semiconductor substrate 10 can be reflected by the silverand can proceed to an inside of the semiconductor substrate 10, therebyincreasing an amount of the light used or available for the solar cell100.

The second electrode 34 may have a width larger than that of the firstelectrode 24.

In the above embodiment of the invention, the semiconductor substrate 10and the back surface field layer 30 are the n-types, and the emitterlayer 20 is the p-type. However, the embodiments of the invention arenot limited thereto. The semiconductor substrate 10 and the back surfacefield layer 30 may be the p-types, and the emitter layer 20 may be then-type. Thus, various modifications are possible.

As in the above, in the solar cell 100 according to the embodiment ofthe invention, a p-n junction or a back surface field structure areformed by a dopant layer such as the emitter layer 20 or the backsurface field layer 30, thereby improving photoelectric conversion inthe solar cell 100. In the embodiment of the invention, out-diffusioncan be prevented and the properties of the dopant layer can be enhancedwhen a dopant layer such as the emitter layer 20 or back surface fieldlayer 30 is formed, and this will be described in detail with referenceto FIG. 2, and FIGS. 3 a to 3 h.

FIG. 2 is a block diagram for illustrating a method for manufacturing asolar cell according to an embodiment of the invention. FIGS. 3 a to 3 hare cross-sectional views for illustrating the method for manufacturingthe solar cell according to the embodiment of the invention.

Referring to FIG. 2, a method for manufacturing a solar cell accordingto the embodiment includes an operation ST10 for preparing asemiconductor substrate, an operation ST20 for forming a dopant layer,an operation ST30 for forming an anti-reflection film and a passivationfilm, and an operation ST40 for forming an electrode.

In this instance, the operation ST20 for forming the dopant layerincludes an operation ST22 for ion-implanting a first conductive typedopant, an operation ST24 for ion-implanting a second conductive typedopant, an operation ST26 for heat-treating for an activation, and anoperation ST28 for cleaning. In the descriptions and drawings, the firstand second conductive type dopants are heat-treated for an activation atthe same time, and thus, the process is simplified. However, theembodiments of the invention are not limited thereto and variousmodifications are possible, and this will be described in more detaillater.

The method for manufacturing the solar cell will be described in moredetail with reference to FIGS. 3 a to 3 h.

First, as shown in FIG. 3 a, in the operation ST10 for preparing thesemiconductor substrate, a semiconductor substrate 10 having a secondconductive type dopant is prepared. The front and back surfaces of thesilicon semiconductor substrate 10 may be textured to have protrudedand/or dented portions of various shapes (or to have an uneven surface).For the texturing method, a wet etching method or a dry etching methodmay be used. In the wet etching method, the substrate 10 may be dippedinto a texturing solution. According to the wet etching method, theprocess time can be short. In the dry etching method, the surface of thesemiconductor substrate 10 is etched by a diamond drill or a laser. Inthe dry etching method, the protruded and/or dented portions can beuniformly formed, though the semiconductor substrate 10 may be damagedand the process time may be long. Alternatively, one of the front andback surfaces of the silicon semiconductor substrate 10 may be texturedby a reactive ion etching. Accordingly, the semiconductor substrate 10may be textured by one or more of various methods.

Next, as shown in FIGS. 3 b to 3 f, an emitter layer 20 and abacksurface field layer 30 that are dopant layers are formed. This will bedescribed in more detail.

As shown in FIG. 3 b, in the operation ST22 for ion-implanting the firstconductive type dopant, a first layer 200 is formed by ion-implanting afirst conductive type dopant to a front surface of a semiconductorsubstrate 10.

Next, as shown in FIG. 3 c, the operation ST24 for ion-implanting thesecond conductive type dopant, a second layer 300 is formed byion-implanting a second conductive type dopant to a back surface of thesemiconductor substrate 10.

Next, as shown in FIGS. 3 d and 3 e, in the operation ST26 forheat-treating for the activation, the first conductive type dopantion-implanted in the operation ST22 for ion-implanting the firstconductive type dopant and the second conductive type dopantion-implanted in the operation ST24 for ion-implanting the secondconductive type dopant are activated by heat-treating for the activationthat anneals the semiconductor substrate 10. Hereby, the emitter layer20 and the back surface field layer 30 that are the dopant layers areformed. This will be described in more detail.

When the first and second conductive type dopants are ion-implanted tothe semiconductor substrate 10, the first and second conductive typedopants are not activated since the dopant are not positioned at thelattice sites. By annealing the semiconductor substrate 10, the firstand second conductive type dopants move to the lattice sites and areactivated. By the activation, the emitter layer 20 is formed from thefirst layer 200 formed at the front surface of the semiconductorsubstrate 10, and the back surface field layer 30 is formed from thesecond layer 300 formed at the back surface of the semiconductorsubstrate 10.

In this instance, in the operation ST26 for heat-treating for theactivation, anti-out-diffusion films 202 and 302 is formed forpreventing out-diffusion of dopants at a temperature lower than thefirst temperature under a first gas atmosphere (FIG. 3 d), and then, thesemiconductor substrate 10 is heat-treated at the first temperature thatis a temperature for the activation (FIG. 3 e).

The specific temperature and condition of the supplied gas in theoperation ST26 for heat-treating for the activation will be described inmore detail with reference to FIG. 4. FIG. 4 is a graph illustrating atemperature with respect to time in the operation ST26 for heat-treatingfor the activation of the method for manufacturing the dopant layeraccording to the embodiment of the invention.

With reference to FIG. 4, the operation ST26 for heat-treating for theactivation according to the embodiment includes an initial region (orinitial duration) IR and a maintaining region (or maintaining duration)MR. In the initial region IR, a temperature increases from a secondtemperature T2 lower than a first temperature T1, which is thetemperature for the activation, to the first temperature T1. In themaintaining region, the first temperature T1 is maintained for apredetermined time. Also, the operation ST26 for heat-treating for theactivation may include a finishing region (or finishing duration) ERwhere a temperature decreases from the first temperature T1 to atemperature lower than the first temperature T1 after the maintainingregion ER. In this instance, the initial region IR includes a firstinitial region (or first initial duration) IR1 and a second initialregion (second initial duration) IR2. In the first initial region IR1, atemperature increases from the second temperature T2 to a thirdtemperature T3. In the second region IR2, a temperature increases fromthe third temperature T3 to the first temperature T1.

As in the above, in the operation ST26 for heat-treating for theactivation, the semiconductor substrate (10 of FIG. 3 d) is insertedinto a heat-treating apparatus which temperature is the secondtemperature T2 lower than the first temperature T1 that is thetemperature for the activation. Then, the temperature increases to thefirst temperature T1, and the heat-treatment for the activation isperformed at the first temperature T1. Then, the temperature decreasesto a temperature lower than the first temperature T1. If thesemiconductor substrate 10 is inserted into the heat-treating apparatuswhich temperature is the first temperature T1 that is the temperaturefor the activation, the semiconductor substrate 10 may be damaged orbroken by a rapid temperature change. Also, if an initial temperature ofthe heat-treating apparatus is a room temperature, much time isnecessary to increase from the room temperature to the first temperatureT1. Thus, the heat-treating is started at the second temperature T2lower than the first temperature T1 in order to prevent a damage of thesemiconductor substrate 10 and to minimize the process time.

For example, the first temperature T1 that is the temperature for theactivation may in a range of about 950° C. to 1300° C. When the firsttemperature T1 is higher than about 1300° C., the semiconductorsubstrate 10 may be damaged and the manufacturing cost may be increaseddue to a high temperature. When the first temperature T1 is lower than950° C., the first and/or second conductive type dopants may beinsufficiently activated.

For example, the second temperature T2 may in a range of about 650° C.to 850° C. When the second temperature T2 is higher than about 850° C.,the semiconductor substrate 10 may be damaged and the manufacturing costmay be increased due to a high temperature. When the second temperatureT2 is lower than 650° C., the process time of the initial region IR maybe increased and the productivity may be reduced.

However, the embodiments of the invention are not limited the abovetemperature. Thus, the first temperature T1 and the second temperatureT2 may be varied.

In the embodiment of the invention, anti-out-diffusion films (202 and302 of FIG. 3 d) are formed by supplying the first gas in at least aregion (in which the temperature increases to the third temperature T3lower than the first temperature T1) of the initial region IR (in whichthe temperature increases from the second temperature T2 to the firsttemperature T1). Then, the heat-treating for the activation is performedat the first temperature T1. Hereby, in the maintaining region MR, theheat-treating for the activation can be performed in the state thatout-diffusion of the dopants doped to the semiconductor substrate 10 isprevented or reduced by the anti-out-diffusion films 202 and 302.

More particularly, the anti-out-diffusion films 202 and 302 are formedby supplying the first gas in the first initial region IR1 in whichtemperature increases from the second temperature T2 to the thirdtemperature T3, as shown in FIG. 3 d. When the first temperature T1 isin a range of about 950° C. to 1300° C. and the second temperature T2 isin a range of about 650° C. to 850° C., the third temperature T3 may bein a range of about 870° C. to 900° C. The third temperature T3 isdetermined or set to be higher than the second temperature T2 and not tothicken the anti-out-diffusion films 202 and 302 excessively. However,the embodiments of the invention are not limited thereto and the thirdtemperature T3 may be varied.

By supplying the first gas in the first initial region IR1 (that is, ata temperature of about 650° C. to 900° C.), the anti-out-diffusion films202 and 302 are formed on surfaces of the semiconductor substrate 10.The first gas may be a material suitable for forming a film by areaction with a material (that is, silicon) included in thesemiconductor substrate 10. For example, the first gas may be oxygensuitable for forming a silicon oxide film by the reaction with thesilicon of the semiconductor substrate 10. In this instance, each of theanti-out-diffusion films 202 and 302 includes an oxide film (moreparticularly, the silicon oxide film).

In the first initial region IR1, another gas (for example, nitrogen) maybe supplied along with the oxygen. If the oxygen that is the first gasis supplied only, the anti-out-diffusion films 202 and 302 may thickenexcessively. This problem may be worsened when a number of thesemiconductor substrate 10 that is processed at a same process or timeis large and an amount of the gas supplied to the heat-treatingapparatus increases. Thus, the nitrogen along with the oxygen issupplied as necessary, and thus, the anti-out-diffusion films 202 and302 having a suitable thickness may be formed on the semiconductorsubstrate 10.

The anti-out-diffusion films 202 and 302 may have thicknesses of about0.1 nm to 20 nm (more particularly, about 1 nm to 5 nm). When theanti-out-diffusion films 202 and 302 may be larger than about 20 nm, theprocess time may increase, and thus, the productivity may decrease andthe properties of the solar cell 100 may be deteriorated. When theanti-out-diffusion films 202 and 302 is smaller than about 0.1 nm, theeffect for preventing the out-diffusion may be insufficient because theanti-out-diffusion films 202 and 302 are thin.

The process time of the first initial region IR1 may be about 1 minuteto 60 minutes (for example, 5 minutes to 60 minutes, and moreparticularly, 5 minutes to 20 minutes). When the process time is smallerthan about 1 minute, the thicknesses of the anti-out-diffusion films 202and 302 may be insufficient. When the process time is larger than about60 minutes, the process time increases, the thicknesses of theanti-out-diffusion films 202 and 302 may be thickened excessively, andthe properties of the solar cell may be deteriorated. The process timeof the first initial region IR1 may be 5 minutes to 20 minutes when thethicknesses of the anti-out-diffusion films 202 and 302 and theproperties of the solar cell 100 are considered. However, theembodiments of the invention are not limited thereto. The process timemay be varied in consideration with the temperature increase speed ofthe first initial region IR1 and thicknesses of the anti-out-diffusionfilms 202 and 302.

In the second initial region IR2 in which temperature increases from thethird temperature T3 to the first temperature T1, a second gas differentfrom the first gas is supplied. More particularly, the second gas hasreactivity with the semiconductor substrate 10 less than that of thefirst gas. Thereby, the anti-out-diffusion films 202 and 302 areprevented from being thickened excessively. The second gas may includethe nitrogen having a relatively small reactivity with the semiconductorsubstrate 10.

As in the above, the embodiment includes the second initial region IR2where the second gas is supplied. However, the embodiments of theinvention are not limited thereto. Thus, the second initial region IR2may be omitted, and the first gas is supplied over the initial regionIR.

Also, in the maintaining region MR where the first temperature T1 ismaintained, the heat-treating for the activation is performed at thetemperature suitable to the heat-treating for the activation. Then, asshown in FIG. 3 e, the emitter layer 20 is formed from the first layer200 formed at the front surface of the semiconductor substrate 10, andthe back surface field layer 30 is formed from the second layer 300formed at the back surface of the semiconductor substrate 10 by theactivation. In this instance, the maintaining region MR may be performedunder the nitrogen atmosphere by supplying the second gas (for example,the nitrogen).

In this instance, the process time of the maintaining region MR may belonger than the process time the initial region (IR) (particularly, thefirst initial region IR1). This is for appropriately controlling theanti-out-diffusion films 202 and 302 and for activating the dopantssufficiently.

In addition, after the maintaining region MR, the finishing region ERfor decreasing the temperature to a temperature lower than the firsttemperature T1 may be performed. Accordingly, when the semiconductorsubstrate 10 is pulled from the heat-treating apparatus, thesemiconductor substrate 10 may be prevented from being damaged orbroken. In the finishing region ER, the second gas may be supplied.

In the embodiment of the invention, in the at least one region of theinitial region IR1 performed before the maintaining region MR, theanti-out-diffusion films 202 and 302 are formed. Accordingly, whensubstantial heat-treating for the activation is performed during themaintaining region MR, the anti-out-diffusion films 202 and 302 preventsthe out-diffusion of the dopants. Therefore, the loss of the dopants canbe minimized, and a doping depth of the dopants can be increased. Thus,a surface recombination velocity (SRV) at the surface of thesemiconductor substrate 10 can be reduced, and a current density (Jsc)and an open-circuit voltage (Voc) of the solar cell 100 can be enhanced.Further, quantum efficiency (particularly, internal quantum efficiency)can be enhanced. Finally, properties and efficiency of the solar cell100 can be enhanced.

Also, the anti-out-diffusion films 202 and 302 are formed by controllinggas supplied in a partial region (or partial duration) of the operationST26 for heat-treating for the activation. Thus, an additional processfor forming the anti-out-diffusion films 202 and 302 is not necessary.That is, the initial region IR where the anti-out-diffusion films 202and 302 are formed and the maintaining region MR where substantialheat-treating for the activation are performed in the same heat-treatingapparatus by a continuous process (an in-situ process). Accordingly, theprocess can be simplified, and the manufacturing cost can be reduced bydecreasing the material cost.

On the other hand, the heat-treating for the activation isconventionally performed in the state that the anti-out-diffusion filmis not formed. Thus, the ion-implanted dopants are out-diffused, andthus, the dopant loss is induced and the doping depth is insufficient.Alternatively, an additional process for forming an anti-out-diffusionfilm is conventionally performed on the surface of the semiconductorsubstrate, whereby the additional process for forming theanti-out-diffusion film is formed by a chemical oxidation using asulfuric acid or a nitric acid. If the additional process is performed,a process is added and the process time is very long (about 20 minutesto 30 minutes), and thus, the productivity is low. Also, high acidity(particularly, similar to an acidity of an undiluted solution) of thesulfuric acid or the nitric acid should be used in order to oxidize thesubstrate. Thus, the material cost is increased, and thus, theproductivity is deteriorated more.

That is, according to the embodiment of the invention, by forming theanti-out-diffusion films 202 and 302 in the operation ST26 forheat-treating for the activation, the surface concentration can bereduced and the doping depth can be increased by preventing theout-diffusion without an additional process. Accordingly, properties ofthe emitter layer 20 and the back surface field layer 30 that are thedopant layers can be enhanced. Thus, properties and efficiency of thesolar cell 100 can be enhanced while increasing productivity.

In the embodiment of the invention, the anti-out-diffusion films 202 and302 are formed to correspond to the emitter layer 20 and the backsurface field layer 30. However, the embodiments of the invention arenot limited thereto. Thus, only the anti-out-diffusion film 202 may beformed for the emitter layer 20, or only the anti-out-diffusion film 302may be formed for the back surface field layer 30.

Next, as shown in FIG. 3 f, in the operation ST28 for cleaning, thesemiconductor substrate 10 that underwent the heat-treating for theactivation is cleaned. In this instance, the anti-out-diffusion films202 and 302 may be eliminated (or removed). In the operation ST28 forcleaning, a diluted hydrofluoric acid (diluted HF) may be used. However,the embodiments of the invention are not limited thereto. Thus, thesemiconductor substrate 10 may be cleaned by using one or more ofvarious materials.

Since the operation ST26 for heat-treating for the activation isperformed at a high temperature, silicate glass (for example, boronsilicate glass (BSG) or phosphorus silicate glass (PSG)) may be formedon the surfaces of the semiconductor substrate 10. Theanti-out-diffusion films 202 and 302 are combined with the silicateglass, and thus, the silicate glass can be eliminated when theanti-out-diffusion films 202 and 302 are eliminated in the operationST28 for cleaning. The properties of the solar cell 100 may be reducedwhen the silicate glass is remained; however, in the embodiment of theinvention, the silicate glass can be eliminated by theanti-out-diffusion films 202 and 302, and thus, the properties of thesolar cell 100 can be improved. In addition, an additional process foreliminating only the silicate glass is not necessary, therebysimplifying the manufacturing process.

Next, as shown in FIG. 3 g, in the operation ST30 for forming ananti-reflection film 22 and a passivation film 32, the anti-reflectionfilm 22 and the passivation film 32 are formed on the front surface andthe back surface of the semiconductor substrate 10, respectively.

The anti-reflection film 22 and the passivation film 32 may be formed byone or more of various methods such as vacuum evaporation, chemicalvapor deposition, spin coating, screen printing, or spray coating.

Next, as shown in FIG. 3 h, in the operation ST40 for forming theelectrodes 24 and 34, a first electrode 24 electrically connected to theemitter layer 20 is formed at the front surface of the semiconductorsubstrate 10 and a second electrode 34 electrically connected to theback surface field layer 30 (or, the semiconductor substrate 10) isformed at the back surface of the semiconductor substrate 10.

After forming an opening at the anti-reflection layer 22, the firstelectrode 24 may be formed inside the opening by one or more of variousmethods, such as a plating method or a deposition method. Also, afterforming an opening at the second passivation layer 32, the secondelectrode 34 may be formed inside the opening by one or more of variousmethods, such as a plating method or a deposition method.

Alternatively, the first and second electrodes 24 and 34 may be formedby fire-through or laser firing contact of printed pastes for the firstand second electrodes 24 and 34. For example, the pastes may be printedby various methods such as a screen printing method. In this instance,because the openings are naturally (or automatically) formed during thefire-through or the laser firing contact, separate operations forforming the openings are not necessary.

The detailed descriptions and the drawings are provided only forsuggesting one example among various embodiments of the invention, andthus, various modifications are possible.

That is, in the embodiments of the invention, after ion-implanting thefirst conductive type dopant, the second conductive type dopant ision-implanted. Then, the first and second conductive type dopants areco-activated. However, the embodiments of the invention are not limitedthereto. Therefore, after ion-implanting the second conductive typedopant, the first conductive type dopant may be ion-implanted. Also, theheat-treating for an activation of the first conductive type dopant andthe heat-treating for an activation of the second conductive type dopantmay be performed separately. In this instance, the heat-treating for theactivation can be preformed to be suitable for properties of thedopants.

Also, in the embodiments of the invention, after forming both of theanti-reflection film 22 and the passivation film 32, the first andsecond electrodes 24 and 34 are formed. However, the embodiments of theinvention are not limited thereto. Accordingly, the anti-reflection film22 may be formed, and then, the first electrode 24 may be formed. Afterthat, the passivation film 32 may be formed, and then, the secondelectrode 34 may be formed. Alternatively, the passivation film 32 maybe formed, and then, the second electrode 34 may be formed. After that,the anti-reflection film 22 may be formed, and then, the first electrode24 may be formed

In the embodiment of the invention, after forming both dopant layers(the emitter layer 20 and the back surface field layer 30), theanti-reflection film 22 and the passivation film 32 are formed. However,the embodiments of the invention are not limited thereto. Therefore, theemitter layer 20 may be formed, and then, the anti-reflection film 22may be formed. After that, the back surface field layer 30 may beformed, and then, the passivation film 32 may be formed. Alternatively,the back surface field layer 30 may be formed, and then, the passivationfilm 32 may be formed. After that, the emitter layer 20 may be formed,and then, the anti-reflection film 22 may be formed.

That is, manufacturing sequence of the emitter layer 20, the backsurface field layer 30, the anti-reflection film 22, the passivationfilm 32, the first electrode 24, and the second electrode 34 may bevariously modified.

Further, the emitter layer 20 and the back surface field layer 30 areexemplified as the dopant layer. However, the embodiments of theinvention are not limited thereto. In a back contact solar cell, thedopant layer may be a front surface field layer doped with a dopant of aconductive type the same as a conductive type of the semiconductorsubstrate.

Hereinafter, a solar cell or a method for forming a solar cell accordingto another embodiment of the invention will be described in more detailwith reference to FIGS. 5 a to 5 e, and FIG. 6. In the followingdescription, any described portions already described above will beomitted, and any portions not already described above will be describedin detail. Also, the modifications of the above embodiment areapplicable to the following embodiment.

FIGS. 5 a to 5 e are cross-sectional views for illustrating a method formanufacturing a solar cell according to another embodiment of theinvention.

As shown in FIG. 5 a, a first layer 200 and a second layer 300 areformed on a semiconductor substrate 10.

As shown in FIG. 5 b, capping layers 204 and 304 are formed on the firstlayer 200 and the second layer 300 on the semiconductor substrate 10,respectively. The capping layers 204 and 304 are oxidation layers formedby a method using a strong acid (for example, a NAOS (nitric acidoxidation of silicon) method using a nitride acid). When the cappinglayers 204 and 304 are further formed as in the above, the out-diffusionof the dopants of the first layer 200 and the second layer 300 can beeffectively prevented.

Next, as shown in FIG. 5 c, an emitter layer 20 and a back surface fieldlayer 30 are formed by activating the dopants after forming theanti-out-diffusion films 202 and 302 in an operation for heat-treatingfor an activation.

Next, as shown in FIG. 5 d, the capping layers 204 and 304, and theanti-out-diffusion films 202 and 302 are eliminated in an operation forcleaning. Next, as shown in FIG. 5 e, an anti-reflection film 22, apassivation film 32, a first electrode 24, and a second electrode 34 areformed.

In the embodiment of the invention, by forming an additional cappinglayers 204 and 304, the out-diffusion of the dopants of the first layer200 and the second layer 300 can be effectively prevented.

FIG. 6 is a cross-sectional view of a solar cell according to anotherembodiment of the invention.

Referring to FIG. 6, in a solar cell according to the embodiment of theinvention, an emitter layer 20 has a selective emitter structure and aback surface field layer 30 has a selective back surface fieldstructure.

In the embodiment of the invention, the emitter layer 20 having theselective emitter structure includes a first portion 20 a being adjacentto and being in contact with the first electrode 24, and a secondportion 20 b other than the first portion 20 a.

The first portion 20 a has a relatively high doping concentration andhas a relatively low resistance, and the second portion 20 b has arelatively low doping concentration and has a relatively highresistance. That is, in the embodiment of the invention, a shallowemitter can be achieved by forming the second portion 20 b having therelatively high resistance at a portion where the sun light is incidentbetween adjacent first electrodes 24, thereby enhancing the currentdensity of the solar cell 100. In addition, contact resistance with thefirst electrode 24 can be reduced by forming the first portion 20 ahaving the relatively low resistance at a portion that is in contactwith the first electrode 24. That is, when the emitter layer 20 has theselective emitter structure, the efficiency of the solar cell 100 can beincreased or maximized.

Thus, the dose of the first conductive type dopant at the first portion20 a may larger than the dose of the first conductive type dopant at thesecond portion 20 b. When there is a dose difference (or to generate adose difference) between the first portion 20 a and the second portion20 b, a comb mask may be used. However, the embodiments of the inventionare not limited thereto. Thus, the number of the ion-implantationprocess may be different at the first and second portions 20 a and 20 b.Other methods may be used.

The back surface field layer 30 having a selective back surface fieldstructure includes a first portion 30 a being adjacent to and being incontact with the second electrode 34, and a second portion 30 b otherthan the first portion 30 a.

The first portion 30 a has a relatively high doping concentration andhas a relatively low resistance, and the second portion 30 b has arelatively low doping concentration and has a relatively highresistance. That is, in the embodiment of the invention, therecombination of the electrons and holes can be reduced or prevented byforming the second portion 30 b having the relatively high resistance ata portion between the adjacent second electrodes 34, thereby enhancingthe current density of the solar cell 100. In addition, contactresistance with the second electrode 34 can be reduced by forming thefirst portion 30 a having the relatively low resistance at a portionthat is in contact with the second electrode 34. That is, when the backsurface field layer 30 has the selective back surface field structure,the efficiency of the solar cell 100 can be increased or maximized.

Thus, the dose of the second conductive type dopant at the first portion30 a may larger than the dose of the second conductive type dopant atthe second portion 30 b. When there is a dose difference (or to generatea dose difference) between the first portion 30 a and the second portion30 b, a comb mask may be used. However, the embodiments of the inventionare not limited thereto. Thus, the number of the ion-implantationprocess may be different at the first and second portions 30 a and 30 b.Other methods may be used.

As such, in the embodiment of the invention, the emitter layer 20 andthe back surface field layer 30 have a selective structure includingportions with different resistances, thereby enhancing the efficiency ofthe solar cell.

In the embodiment of the invention, both of the emitter layer 20 and theback surface field layer 30 have the selective structure. However, theembodiments of the invention are not limited thereto. Therefore, one ofthe emitter layer 20 and the back surface field layer 30 may have theselective structure.

Hereinafter, the embodiments of the invention will be described in moredetail through experimental embodiments. The experimental embodimentsare provided only for illustrative purpose of the embodiments of theinvention, and the embodiments of the invention are not limited thereto.

Experimental Embodiment 1

An n-type semiconductor substrate was prepared. Boron as a firstconductive type dopant was ion-implanted to the front surface of thesemiconductor substrate, and phosphorus as a second conductive typedopant was ion-implanted to the back surface of the semiconductorsubstrate. The semiconductor substrate to which the ion-implanting wasperformed was put to a heat-treating apparatus for an activation. Thetemperature increased from 720° C. to 900° C. while supplying oxygen for50 minutes, thereby forming an oxide film. Then, the temperatureincreased to 1050° C. and was maintained while supplying nitrogen, andthe boron and the phosphorus were activated, thereby forming an emitterlayer and a back surface field layer. After that, the oxide film waseliminated by cleaning using a diluted HF.

An anti-reflection film was formed on the front surface of thesemiconductor substrate, and a passivation film was formed on the backsurface of the semiconductor substrate. Then, a first electrodeelectrically connected to the emitter layer and a second electrodeelectrically connected to the back surface field layer were formed, anda solar cell was manufactured.

Experimental Embodiment 2

A solar cell was manufactured by the same method as ExperimentalEmbodiment 1 except for a method forming the oxide film. In ExperimentalEmbodiment 2, capping layers of oxide were formed by using a nitric acidfor 25 minutes after ion-implanting the first and second conductive typedopants, and then, an oxide film was formed in the heat-treatingapparatus for the activation for 25 minutes. That is, ExperimentalEmbodiment 2 is different from Experimental Embodiment 1 in that thecapping layer existed along with the oxide film as theanti-out-diffusion film and the process time for forming the oxide filmin the heat-treating for the activation was 25 minutes. In the step forcleaning, the capping layer, along with the oxide film, was eliminated.

Experimental Embodiment 3

A solar cell was manufactured by the same method as ExperimentalEmbodiment 1 except that the oxide film was formed for 10 minutes in theheat-treating for the activation.

Experimental Embodiment 4

A solar cell was manufactured by the same method as ExperimentalEmbodiment 1 except that the oxide film was formed for 5 minutes in theheat-treating for the activation.

Comparative Example

An n-type semiconductor substrate was prepared. Boron as a firstconductive type dopant was ion-implanted to the front surface of thesemiconductor substrate, and phosphorus as a second conductive typedopant was ion-implanted to the back surface of the semiconductorsubstrate. Capping layers of oxide were formed on surfaces of thesemiconductor substrate by using a nitric acid for 25 minutes. Thesemiconductor substrate to which the ion-implanting was performed wasput to a heat-treating apparatus for an activation. The temperatureincreased from 720° C. to 1050° C. and was maintained at 1050° C. whilesupplying nitrogen, and the boron and the phosphorus were activated,thereby forming an emitter layer and a back surface field layer. Afterthat, the oxide film was eliminated by cleaning using a diluted HF.

An anti-reflection film was formed on the front surface of thesemiconductor substrate, and a passivation film was formed on the backsurface of the semiconductor substrate. Then, a first electrodeelectrically connected to the emitter layer and a second electrodeelectrically connected to the back surface field layer were formed, anda solar cell was manufactured.

Reflectance with respect to wavelength, external quantum efficiency, andinternal quantum efficiency of the solar cells manufactured byExperimental Embodiments 1 and 2, and Comparative Example were detected.The results are shown in FIGS. 7, 8, and 9, respectively. Also, FIGS. 10and 11 are enlarged views of portions A and B of FIG. 9, respectively.

Referring to FIG. 7, it can be seen that reflectance of the solar cellsaccording to Experimental Embodiments 1 and 2 in short wavelengths andin long wave lengths is different from reflectance of the solar cellaccording to Comparative Example. Accordingly, it can be seen thatmorphology of the surfaces of the solar cells of ExperimentalEmbodiments 1 and 2 are changed. For reference, although the reflectanceof the solar cells of Experimental Embodiments 1 and 2 increasesslightly, it does not affect the efficiency of the solar cells.

Referring to FIGS. 8 and 9, the solar cells of Experimental Embodiments1 and 2 have highly-enhanced quantum efficiency (particularly, internalquantum efficiency), compared with Comparative Example. As shown in FIG.10, the solar cells of Experimental Embodiments 1 and 2 have enhancedinternal quantum efficiency in the short wavelengths, compared withComparative Example. As shown in FIG. 11, the solar cells ofExperimental Embodiments 1 and 2 have enhanced internal quantumefficiency in the long wavelengths, compared with Comparative Example.When the current density (Jsc) is calculated by the internal quantumefficiency, the current density in wavelengths of 300˜800 nm ofExperimental Embodiments 1 and 2 increases by about 0.15 mA/cm², and thecurrent density in wavelengths of 800˜1200 nm of ExperimentalEmbodiments 1 and 2 increases by about 0.22 mA/cm².

Also, the sheet resistances of the emitter layers of the solar cellsaccording to Experimental Embodiments 1 and 2, and Comparative Examplewere measured, and the results are shown in FIG. 12. The sheetresistances of the back surface field layers of the solar cellsaccording to Experimental Embodiments 1 and 2, and Comparative Examplewere measured, and the results are shown in FIG. 13. The implied Voc ofthe solar cells according to Experimental Embodiments 1 and 2, andComparative Example were measured, and the results are shown in FIG. 14.The sheet resistances and the implied Voc are shown as relative values.

Referring to FIGS. 12 and 13, it can be seen that the solar cellsaccording to Experimental Embodiments 1 and 2 has high sheet resistancesof the emitter layer and the back surface field layer, Compared withComparative Example. Accordingly, the surface recombination velocity canbe reduced. In addition, referring to FIG. 14, it can be seen that theimplied Voc of the solar cells according to Experimental Embodiments 1and 2 is improved, compared with Comparative Example. Accordingly,according Experimental Embodiments 1 and 2, various properties of thedopant layers can be improved and efficiency of the solar cells can beenhanced.

Furthermore, six solar cells were manufactured according to ComparativeExample and twelve solar cells were manufactured according toExperimental Embodiment 1. In the solar cells, the emitter layers wereformed and the cleansings were performed. The solar cells are shown inFIG. 15. As shown in FIG. 15, in the solar cells according toComparative Example, chemical materials (for example, boron silicateglass, (BSG)) are remained on the surfaces of the substrate. On theother hand, in the solar cells according to Experimental embodiment 1,chemical materials (for example, boron silicate glass, BSG)) are notremained on the surfaces of the substrate. This is because the silicateglass was also eliminated when the anti-out-diffusion film waseliminated. Therefore, according to Experimental Embodiment 1, thesilicate glass can be eliminated, thereby enhancing properties of thesolar cell.

In addition, measured values of thicknesses of the oxide films (that is,the anti-out-diffusion film) of the solar cells according toExperimental Embodiments 3 and 4 are shown in Table 1, along withtheoretical values.

TABLE 1 Theoretical value Measured value [nm] [nm] ExperimentalEmbodiment 3 1.6 5.168 Experimental Embodiment 4 0.8 4.838

Referring to Table 1, it can be seen that the oxide films according toExperimental Embodiments 3 and 4 have thickness larger than thetheoretical values. That is, according to the embodiment of theinvention, the oxide film having sufficient thickness can be formed by asimple process (that is, supplying the oxygen in the step forheat-treating for the activation), and thus, the oxide film can act asthe anti-out-diffusion film.

Also, open-circuit voltages (Voc), current densities (Jsc), fillfactors, and efficiencies of forty six solar cells manufacturedaccording to Experimental Embodiment 3 and forty four solar cellsmanufactured according to Comparative Example were measured, and averagevalues thereof are shown in Table 2.

TABLE 2 Open-circuit Current Fill factor Efficiency voltage (Voc)density (Jsc) [%] [%] Experimental 650.4 39.33 79.17 20.25 Embodiment 3Comparative 647.6 39.26 79.03 20.09 Example

Referring to Table 2, it can be seen that the solar cells according toExperimental Embodiment 3 have enhanced open-circuit voltage, currentdensity, fill factor, and efficiency. Particularly, the open-circuitvoltage in Experimental Embodiment 3 is larger than that in ComparativeExample by about 3 mV, and is very superior than that in ComparativeExample. Also, the efficiency in Experimental Embodiment 3 is largerthan that in Comparative Example by about 0.15%, and is superior thanthat in Comparative Example.

The dopant concentration with respect to the junction depths of theemitter layers in the solar cells manufactured according to ExperimentalEmbodiment 3 and Comparative Example were measured. The result is shownin FIG. 16. In this instance, dopant amounts of the emitter layers areshown in Table. 3. An electrochemical capacitance-voltage (ECV) profilewas measured and then was compensated by using an area and a sheetresistance. After the compensating the profile, the dopant amounts inTable 3 is calculated.

TABLE 3 Dopant amount Experimental Embodiment 3 1.24 × 10¹⁵ ComparativeExample 1.02 × 10¹⁵

Referring to Table 3, it can be seen that the dopant amount inExperimental Embodiment 3 is larger than the dopant amount inComparative Example. Also, referring to FIG. 16, it can be seen that thedopants are uniformly distributed with a higher concentration at thesurface of the semiconductor substrate (that is, the surface of theemitter layer) in Experimental Embodiment 3 than Comparative Example.That is, it is can be expected that more carriers can be formed and becollected at the surface of the semiconductor substrate and theefficiency of the solar cell can be enhanced. It is expected that thisis because the oxide film formed by the thermal method has a densitylarger than a density of the oxide film formed by the chemical method.

According to the embodiment of the invention, by forming theanti-out-diffusion films in the step for heat-treating for theactivation, the surface concentration can be reduced and the dopingdepth can be increased by preventing the out-diffusion without anadditional process. Accordingly, properties of the dopant layers (forexample, the emitter layer, the front surface field layer, and the backsurface field layer) can be enhanced. Thus, properties and efficiency ofthe solar cell can be enhanced while increasing productivity.

Certain embodiments of the invention have been described. However, theinvention is not limited to the specific embodiments described above,and various modifications of the embodiments are possible by thoseskilled in the art to which the invention belongs without leaving thescope defined by the appended claims.

What is claimed is:
 1. A method for manufacturing a dopant layer of asolar cell, the method comprising: ion-implanting a dopant to asubstrate; and heat-treating for an activation of the dopant, whereinthe heat-treating for the activation comprises: an initial durationhaving a first initial duration for forming an anti-out-diffusion filmunder a first gas atmosphere comprising oxygen; and a maintainingduration for activating the dopant at a first temperature after theinitial duration, wherein the initial duration is composed of atemperature increase region of the heat-treating for the activationunder a temperature lower than the first temperature before themaintaining duration, wherein the maintaining duration is performed onlyafter the first initial duration, wherein the first initial duration andthe maintaining duration are parts of an in-situ process, wherein theinitial duration further comprises a second initial duration after thefirst initial duration, in the first initial duration, a temperatureincreases from a second temperature lower than the first temperature toa third temperature higher than the second temperature and lower thanthe first temperature, in the second initial duration, a temperatureincreases from the third temperature to the first temperature, andwherein a second gas atmosphere different from the first gas atmosphereis supplied in the second initial duration.
 2. The method according toclaim 1, wherein the anti-out-diffusion film comprises an oxide film. 3.The method according to claim 2, wherein nitrogen is supplied with theoxygen in the first initial duration.
 4. The method according to claim1, wherein the maintaining duration is performed under the second gasatmosphere different from the first gas atmosphere.
 5. The methodaccording to claim 4, wherein the second gas atmosphere comprisesnitrogen.
 6. The method according to claim 1, wherein a process time ofthe maintaining duration is longer than a process time of the firstinitial duration.
 7. The method according to claim 1, wherein a processtime of the first initial duration is in a range of about 1 minute toabout 60 minutes.
 8. The method according to claim 1, wherein the secondgas atmosphere is supplied in the maintaining duration.
 9. The methodaccording to claim 1, wherein the heat-treating for the activationfurther comprises a finishing duration where a temperature decreasesafter the maintaining duration.
 10. The method according to claim 1,wherein the initial duration and the maintaining duration areconsecutively performed in a same heat-treating apparatus.
 11. Themethod according to claim 1, wherein the first temperature is in a rangeof about 950° C. to 1300° C.
 12. The method according to claim 1,wherein a temperature in the first initial duration is in a range ofabout 650° C. to 900° C.
 13. The method according to claim 1, whereinthe anti-out-diffusion film has a thickness of about 0.1 nm to 20 nm.14. The method according to claim 1, further comprising cleaning thesubstrate after the heat-treating for the activation, wherein theanti-out-diffusion film is eliminated in the cleaning.
 15. The methodaccording to claim 14, wherein silicate glass is formed on a surface ofthe substrate in the heat-treating for the activation, and the silicateglass formed on the surface of the substrate is eliminated with theanti-out-diffusion film during the cleaning.
 16. The method according toclaim 1, further comprising forming a capping layer on a surface of thesubstrate between the ion-implanting and the heat-treating for theactivation, wherein the anti-out-diffusion film is formed on the cappinglayer during the heat-treating for the activation.
 17. A method formanufacturing a solar cell, the method comprising: performing the methodfor manufacturing the dopant layer according to claim 1; and forming anelectrode electrically connected to the dopant layer.
 18. The methodaccording to claim 17, wherein the dopant layer is at least one of anemitter layer, a front surface field layer, and a back surface fieldlayer.